JPS6291901A - Production of glass lens having dyed hardening surface layer - Google Patents

Abstract

PURPOSE:To easily produce the hyperchromic glass lens having various kinds of color by coating a solution for an org. hard film contg. a specific hydrolysis condensate as a main component on the surface of the glass lens and then by hardening it followed by dyeing it with a dyeing bath contg. a cationic dye at a specific temperature. CONSTITUTION:The titled glass lens is produced by coating the solution for the org. hard film contg. the hydrolysis condensate shown by formula (1) or (2) as the main component on the surface of the glass lens and by hardening it followed by dyeing the glass lens having the obtd. hardened surface layer thereon using the dyeing bath contg. 0.001-5wt% of the cationic dye at a temp. of preferably 80-120 deg.C. As an alkoxysilane shown by formula (1), one may use methyltrimethoxysilane. As an alkoxysilane shown by formula (2), one may use tetramethoxysilane, etc. If the dying bath contains <=0.001wt% of the dye, the dyeing rate is too late for a practical application. If the dying bath contains >=5wt% of the dye, as the dye easily sticks to the surface to be dyed, and a dependency of the dye concentration about the dyeing rate is almost lost, it makes difficult to freely color by compounding various kinds of dyes for the practical application.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a colored glass lens, and more particularly to a method for manufacturing a colored glass lens having a dyed and hardened surface layer.

[Conventional technology]

(It has excellent physical properties such as the hardness of the glass lens surface for Iim, which makes it difficult to scratch, and the small deformation due to rigidity, which allows it to maintain a thin shape. However, synthetic resins (e.g. diethylene glycol bisallyl carbonate) 1.)
Compared to lenses, they have the disadvantage of being dyed and having irregularities.

Methods for coloring glass lenses include attaching a coloring substance to the surface of the glass lens by vacuum evaporation, etc., adding a coloring substance during the melting process of glass lens manufacturing to give the glass composition itself coloring properties, and 1986-1990
A method of forming a polymer coating on the concave surface of a glass lens and dyeing it with a disperse dye, as disclosed in Japanese Patent No. 422, has been proposed.

[Problems to be solved by the invention] In the first two methods of directly coloring the glass, the coloring substances are limited and it is not possible to produce any color freely, the coloring density is limited, and the coloring requires a complicated manufacturing process. There were problems such as the need for advanced technology.

In the latter method, in which a polymer film is provided on the surface and dyed, a polymer is used that has sufficient film hardness and satisfies the conditions that film performance such as film hardness and adhesion does not change before and after dyeing. A coating composition and surface treatment method have not yet been discovered, and coating films containing epoxy-containing alkoxysilanes, colloidal silica, etc. as main components cannot be used with disperse dyes normally used for dyeing plastic lenses for eyeglasses.
There was a problem that it was difficult to dye.

[Means for solving problems]

The present invention solves the above problems.

That is, the present invention comprises (a) a step of preparing an organic hard film solution containing the following hydrolyzed condensate as a main component; ('b)
A step of applying and curing the organic hard film solution on the surface of the glass lens, and a step (C) of applying the glass lens having the hardened surface layer obtained in step (bl) to a dye bath of a cationic dye at a concentration of 0.001 to 5% by weight. The present invention also relates to a method for manufacturing a glass lens having a dyed and hardened surface layer, which comprises a step of dyeing at a temperature of 40 to 100°C using a dyed and hardened surface layer.

General formula (1) %Formula % (1) [However, R, is an alkyl group having 1 to 4 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms, -CH=CHz, and a selected organic group. ] A hydrolyzed condensate of at least one alkoxysilane represented by or at least one of the above alkoxysilanes
A hydrolyzed condensate of a species and an alkoxysilane or colloidal silica represented by the general formula (2) % formula % (2) [wherein is an alkyl group having 1 to 4 carbon atoms].

The organic hard film solution used in the present invention consists of the above hydrolyzed condensate as main components, a curing agent, and a solvent.

Examples of the alkoxysilane represented by the general formula (1) in the present invention include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-gu, 1 1'xypropyltriethoxysilane, T-methacryloxypropyltrimethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyl Examples include trimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, T-chloropropyltrimethoxysilane, and T-mercaptopropyltriethoxysilane.

Examples of the alkoxysilane represented by the general formula (2) include tetramethoxysilane and tetraethoxysilane.

The colloidal silica preferably has a particle size of approximately 5 mμ to 30 mμ when dispersed in water or alcohol.

As the acid for hydrolyzing these alkoxysilanes or colloidal silicas, hydrochloric acid and acetic acid are preferred.

Although imidazole derivatives and the like are available as curing agents used in organic hard film solutions containing alkoxysilane or colloidal silica as a main component, acetylacetone metal salts are particularly effective.

The amount added is sufficient to cure a hydrolyzed condensate of an organosilicon compound of colloidal silica and alkoxysilane, for example, a total of 1 mole of the hydrolyzed condensate of colloidal silica (Sin, conversion), alkoxysilane, etc. 1 to 10 g.

Examples of the solvent used in the organic hard film solution include lower alcohols, esters, ethers, ketones, etc., and isopropyl alcohol, butanol, methyl cellofulve, etc. are particularly preferred.

A silicone surfactant can also be added to the organic hard film solution, ie, the coating liquid, for the purpose of improving the smoothness of the coating film. Furthermore, it is also possible to add ultraviolet absorbers, antioxidants, etc. for the purpose of improving weather resistance or preventing deterioration of the coating film.

Furthermore, various additives can be added for the purpose of improving practicality such as improving adhesion with glass lenses and improving physical properties.

Further, it is not preferable to add sodium acetate, which is generally used to stabilize the pH of the coating liquid or as a catalyst. The reason for this is that sodium acetate tends to precipitate toward the film surface after the coating composition is applied and cured, which has a negative effect on the film formation of vapor-deposited substances.Also, the lens surface must be cleaned with a hand wipe or washed before vapor deposition. This is because even if it is mixed, it will precipitate in a vacuum or during heating and will have a similar adverse effect.

Coating methods for applying and curing the silicone-based organic hard film solution on the surface of the glass lens include generally used dipping method, spin coater method, roll coater method, spray method, etc. It will be done.

Hardening of the surface film is mainly performed by heat treatment.

Although the heating temperature can vary over a wide range, it is preferably 40 to 150°C, particularly preferably 80 to 120°C. A heating time of 1 to 4 hours or more gives good results.

Before applying the coating liquid, the plastic lens is preferably pretreated by an alkali treatment, plasma treatment, ultraviolet irradiation treatment, or the like.

The organic hard coat film obtained by heat curing treatment is
Excellent wear resistance (hardness) and flexibility (flexibility)
It also has excellent heat resistance and chemical (alkali) resistance.

As the cationic dye used in the present invention to dye the organic hard film, all so-called cationic dyes can be used. Cationic dyes are basic dyes that have excellent dyeability and fastness, especially for acrylic fibers, and are generally called cationic dyes.The onium group and the color-forming resonance system are conjugated. They are broadly classified into conjugated type and insulated type depending on whether or not they are present.

In the fal conjugated type, positive charges are distributed throughout the dye matrix, and a quaternary ammonium group is contained in a chain of conjugated double bonds.

(Example) C, 1, Red 13: Most cationic dyes, including conventional basic dyes, belong to this group, and are characterized by bright hues and high tinting power.

The insulated type has positive charges locally localized in the pigment matrix, and its color tone is similar to that of disperse dyes, and even in light colors, it has particularly high fastness (often used for medium-light and intermediate color dyeing.

Commercially available products include, for example, the following.

Eight fzen Cathilon (Hodogaya) Dia
cryl (Mitsubishi) Sumiacryl (Sumitomo)
Kayacryl C8) Astrazo
n (PBY) Maxflon (C
G) Basacryl (BASF) The preferred dye concentration of the dyeing bath is 0.001 to 5% by weight, and the dyeing temperature used is 40°C to 100°C. If the concentration is less than 0.001% by weight, the dyeing speed is too slow for practical purposes, and if it exceeds 5% by weight, the dye not only tends to stick to the surface to be dyed, but the dyeing speed has almost no concentration dependence, so it is not practical. When top dye is added, colors cannot be produced freely. Furthermore, if the dyeing temperature is less than 40°C, the dyeing speed is too slow, and there is no need to exceed 100°C.

As the material for the glass lens used in the present invention, any inorganic glass can be used as long as it has the characteristics of normal glass lenses such as surface precision, surface cleanliness, and heat resistance, and coating with the hard film of the present invention is possible. be. For example, commonly used UV glasses (mainly containing silicon oxide, boron oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, barium oxide, lead oxide, cerium oxide, etc.) and high refractive index lenses ( LHI-IIn lenses (manufactured by Hoya, whose main components are silicon oxide, titanium oxide, sodium oxide, potassium oxide, etc.) are preferably used.

The hard coat film thickness is preferably 0.1 to 10μ, particularly preferably 1 to 5μ. If the film thickness is too thick, it will affect the optical surface of the lens, and problems such as image distortion and aberration will likely occur, and the dyeing time will also become longer, causing problems in productivity. Also, 0
．． If it is less than 1 μm, a dyed layer is formed within the film, making it difficult to obtain suitable dyeing density and color, which is not preferable.

〔Example〕

Production Example Production of Organic Hard Film Solution An aqueous solution of 472 parts by weight of T-glycidoxypropyltrimethoxysilane, 2.0 parts by weight of 0.5N hydrochloric acid, 20 parts by weight of acetic acid, and 100 parts by weight of water was prepared at room temperature. The mixture was stirred for an hour and left at room temperature for 16 hours. To this hydrolysis solution, add 120 fR parts of isopropyl alcohol and 12 parts of butyl alcohol.
0 ffi amount, 16 parts by weight of aluminum acetylacetone, 0.2 parts by weight of silicone surfactant, and 0.1 part by weight of ultraviolet absorber, and after stirring for 8 hours, the mixture was heated at room temperature for 24 hours.
A coating composition was obtained by aging for a period of time.

Production Example 2 Production of Hard Film Coated Lens The coating composition obtained in Production Example 1 was added to LHl-
n lens (HOY A (high refractive index glass lens made by m)
It was coated on the surface of the lens by dipping and pulling up, and 1) was heated and cured at 0° C. for 2 hours to obtain a hard coat lens. The film thickness was 3μ.

Example 1 Dyeing of hard film coated lenses Three hard film coated lenses obtained in Production Example 2 were dyed with the following No.
, 0.1 g/ff of cationic dye shown in 1 to 3, 1 water
) for 10 minutes at 80°C.

The spectral transmittance curves are shown as No. 1.2.3 in FIG. 1 in order.

No, L: Mitsubishi Kasei side Diacryl Yellow
Au-N %No, 2: Diacryl manufactured by Mitsubishi Kasei ■
Red Au-N.

No. 3: Diacryl Blue manufactured by Mitsubishi Kasei@
Au-N.

Example 2 An example of dyeing by combining three primary color dyes of red, yellow, and blue is shown. Generally, all colors can be produced freely by mixing the three primary color dyes.

No. 4: Mixed dye ■ (green) Diacryl Yellow Au-N
O, 2g Diacryl
Blue Au-N
O, 2g water 1
2 No. 5: Compound dye■ (for gray) Diac
ryl Yellow
O, 2gDiacryl Red
0.13g Diacryl Bl
ue 0.2g water
1) Compound dye■,■
The lens of Production Example 2 was dyed using the dye at 80°C for 10 minutes. The spectral transmittance curve is shown in FIG. Curve 4 shows No. 4, and curve 5 shows No. 5.

Example 3 Diacr was added to the hard film coated lens obtained in Production Example 2.
Table 1 shows the transmittance of the product at 540 nm after dyeing with yl Red Au-N at different dye concentrations and dyeing temperatures in the dye bath.

(Margin below) Table 1 Example 4 The coating composition obtained in Production Example 1 was applied to the surface of the U lens (crown glass) by dipping and pulling up.
) A hard lens was obtained by heating and curing at 0° C. for 2 hours. The film thickness was 3μ.

Next, three hard lenses obtained by the above method were dyed with the following cationic dye 0.1g/A' and water 1β in a staining solution of 80%.
Staining was carried out at ℃ for 10 minutes. The spectral transmission curve is shown as No. 9.10.1) in FIG. 3.

No. 9: Diacryl Yellow manufactured by Mitsubishi Kasei@
AU-N %No, 10: Diacry manufactured by Mitsubishi Kasei ■
l Red ALI-NsNo, 1): D made by Mitsubishi Kasei ■
iacryl Blue AU-N.

The spectral transmittance curves shown in FIGS. 1 to 3 show that the material is dyed in a deep color due to absorption at the wavelength of each color.

Note that Table 2 shows the results of the performance test after dyeing the coating film in the Examples.

Table 2 Note that the performance test of the coating film of the example was conducted as follows.

fa+ Additional load 2 applied to the surface using steel wool with abrasion resistance #0000
00g, 1000 times (back and forth) and the abrasion resistance was evaluated as follows.

A: There is almost no damage.

B: Slight damage.

C: Many scratches occur.

D=Peeling of the film occurs.

(1)) Adhesion According to JIS-Z-1522, 10×1
A peel test was performed three times using zero-piece cellophane adhesive tape, and the number of remaining goblets was determined.

(C) Heat Resistance, Hot Water Resistance ■ A plastic lens coated with the coating composition of the present invention, cured and dyed was placed in a constant temperature oven at 150°C, and it was examined whether or not cranks would enter the coating film.

■ The samples were immersed in boiling water for 1 hour and examined for any changes in appearance.

〔Effect of the invention〕

According to the method of the present invention, dark glass lenses of various colors can be easily obtained.

[Brief explanation of drawings]

FIG. 1.2.3 shows the spectral transmittance curve of a glass lens having a dyed and hardened surface layer according to an example of the present invention.

Claims (1)

[Claims] (1) (a) A step of preparing an organic hard film solution containing the hydrolyzed condensate shown below as a main component, (b) A step of applying and curing the organic hard film solution on the surface of a glass lens,
and (c) dyeing the glass lens having the hardened surface layer obtained in step (b) using a dyebath of a cationic dye at a concentration of 0.001 to 5% by weight at a temperature of 40 to 100°C. A method for manufacturing a glass lens having a dyed and hardened surface layer, characterized in that: General formula (1) R_2-Si-(OR_1)_3(1) [However, R_1 is an alkyl group having 1 to 4 carbon atoms, R_2 is an alkyl group having 1 to 4 carbon atoms, -CH=CH_2, ▲ Formula, There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, -CH_2CH_2CH_2SH,
-CH_2CH_2CH_2Cl, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_2CH_2CH_2NH_2
, -CH_2CH_2CH_2NHCH_2CH_2N
It is an organic group selected from H_2. ] A hydrolyzed condensate of at least one alkoxysilane represented by or at least one of the above alkoxysilanes
Species and general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) [However, R_4 is an alkyl group having 1 to 4 carbon atoms] Hydrolyzed condensate with alkoxysilane or colloidal silica .